Phenalenannulations: Three-Point Double Annulation Reactions that Convert Benzenes into Pyrenes

3-Point annulations, or phenalenannulations, transform a benzene ring directly into a substituted pyrene by “wrapping” two new cycles around the perimeter of the central ring at three consecutive carbon atoms. This efficient, modular, and general method for π-extension opens access to non-symmetric pyrenes and their expanded analogues. Potentially, this approach can convert any aromatic ring bearing a -CH₂Br or a -CHO group into a pyrene moiety. Depending upon the workup choices, the process can be directed towards either tin- or iodo-substituted product formation, giving complementary choices for further various cross-coupling reactions. The two-directional bis-double annulation adds two new polyaromatic extensions with a total of six new aromatic rings at a central core.     

The pyrolysis of propane

The pyrolysis of propane plays an important role in determining the combustion properties of natural gas mixtures and offers insight into the cracking patterns of larger fuels. This work investigates propane pyrolysis behind reflected shock waves with a multiwavelength laser-absorption speciation technique. Nine laser wavelengths, sensitive to key pyrolysis species, were used to measure absorbance time histories during the decomposition of 2% propane in argon between 1022 and 1467 K, 3.7-4.3 atm. Absorbance models were developed at each diagnostic wavelength to interrogate common initial conditions, and time histories of all major species are reported at 1250, 1290, 1330, 1370, and 1410 K. Nearly complete carbon recovery observed at lower temperatures enabled the inference of hydrogen formation from atomic conservation, while decaying carbon recovery at high temperatures suggests the formation of allene and 1-butene. The results show systematically faster pyrolysis than predicted by kinetic modeling and motivate further study into the kinetics of propane pyrolysis.     

The Expanded Genetic Alphabet

All biological information, since the last common ancestor of all life on Earth, has been encoded by a genetic alphabet consisting of only four nucleotides that form two base pairs. Long‐standing efforts to develop two synthetic nucleotides that form a third, unnatural base pair (UBP) have recently yielded three promising candidates, one based on alternative hydrogen bonding, and two based on hydrophobic and packing forces. All three of these UBPs are replicated and transcribed with remarkable efficiency and fidelity, and the latter two thus demonstrate that hydrogen bonding is not unique in its ability to underlie the storage and retrieval of genetic information. This Review highlights these recent developments as well as the applications enabled by the UBPs, including the expansion of the evolution process to include new functionality and the creation of semi‐synthetic life that stores increased information.     

The Cancer Genetics Network: recruitment results and pilot studies

OBJECTIVE: The National Cancer Institute established the Cancer Genetics Network (CGN) to support collaborative investigations into the genetic basis of cancer susceptibility, explore mechanisms to integrate this new knowledge into medical practice, and identify ways of addressing the associated psychosocial, ethical, legal, and public health issues. SUBJECTS AND METHODS: The CGN has developed the complex infrastructure required to support the projects, including the establishment of guidelines and policies, uniform methods, standard questionnaires to be used by all of the centers, and a standard format for submission of data to the Informatics Center. Cancer patients and their family members have been invited to enroll and be included in a pool of potential study participants. The Information Technology Group is responsible for support of the design, implementation, and maintenance of the multicenter Network-wide research protocols. RESULTS: As of January 2004, the CGN contained data on 23,995 probands (participants) and 425,798 family members. As a resource for cancer genetic studies, the CGN has a large number of probands and first-degree relatives with and without cancer and with multiple ethnicities. Different study designs can be used including case-control, case-case, and family studies. CONCLUSIONS: The unique resources of the CGN are available for studies on cancer genetic susceptibility, translational research, and behavioral research. The CGN is now at a point where approved collaborators may have access to enrolled patients and their families for special studies, as well as to the clinical, environmental and family cancer history data banked in the Informatics Center.     

Genetics in primary care: a USA faculty development initiative

The Genetics in Primary Care (GPC) project is a USA national faculty development initiative with the goal of enhancing the training of medical students and primary care residents by developing primary care faculty expertise in genetics. Educational strategies were developed for the project by an executive committee with input from an advisory committee, comprising individuals with primary care, medical education and genetics expertise. These committees identified the key issues in genetics education for primary care as (1) considering inherited disease in the differential diagnosis of common disorders; (2) using appropriate counseling strategies for genetic testing and diagnosis, and (3) understanding the implications of a genetic diagnosis for family members. The group emphasized the importance of a primary care perspective, which suggests that the clinical utility of genetic information is greatest when it has the potential to improve health outcomes. The group also noted that clinical practice already incorporates the use of family history information, providing a basis for discussing the application of genetic concepts in primary care. Genetics and primary care experts agreed that educational efforts will be most successful if they are integrated into existing primary care teaching programs, and use a case-based teaching format that incorporates both clinical and social dimensions of genetic disorders. Three core clinical skills were identified: (1) interpreting family history; (2) recognizing the variable clinical utility of genetic information, and (3) acquiring cultural competency. Three areas of potential controversy were identified as well: (1) the role of nondirective counseling versus shared decision-making in discussions of genetic testing; (2) the intrinsic value of genetic information when it does not influence health outcomes, and (3) indications for a genetics referral. The project provides an opportunity for ongoing discussion about these important issues.     

Shock tunnel flow visualization using planar laser-induced fluorescence imaging of NO and OH

Temporal sequences of planar laser-induced fluorescence (PLIF) images of several high-speed, transient flowfields created in a reflection-type shock tunnel facility were acquired. In each case, the test gas contained either nitric oxide or the hydroxyl radical, the fluorescent species. The processes of shock reflection from an endwall with a converging nozzle and of underexpanded free jet formation were examined. A comparison was also made between PLIF imaging and shadow photography. The investigation demonstrated some of the capabilities of PLIF imaging diagnostics in complex, transient, hypersonic flowfields, including those with combustion.Nomenclature A spontaneous emission rate - A _las cross sectional area of laser sheet - B laser absorption rate - C _opt constant dependent on optical arrangement, collection efficiency, etc. - D nozzle throat diameter - E _p laser pulse energy - f _J Boltzmann fraction of absorbing state - g spectral convolution of laser and absorption lineshapes - k Boltzmann constant - M _s incident shock Mach number - N noise, root-mean-square signal fluctuation - P static pressure - P ₁ initial pressure of test gas in shock tube - P _a free jet ambient pressure - P _s stagnation pressure - Q electronic quenching rate of excited state - S PLIF signal - t time between shock reflection and image acquisition - T static temperature - T _s stagnation temperature - _a mole fraction of absorbing species     

cis,trans-1,5-Cyclodecadiene—Sulfur Dioxide Copolymer

An alternating linear copolymer of cis,trans-1,5-cyclodecadiene and sulfur dioxide has been prepared in quantitative yield. Transannular carbon-carbon bond formation gives four saturated carbon atoms between the sulfone groups. The polymer is resistant to alkali but degrades thermally above 150°C with random chain cleavage.     

Measurement of time histories of stable intermediates during first stage ignition of n-heptane and its two isomers in a shock tube

We report the first shock tube measurements of formaldehyde (CH₂O) during the first stage ignition of n-heptane, 2-methylhexane and 3,3-dimethylpentane, in highly diluted fuel/oxygen mixtures in the pressure range of 7–10 atm and temperature range of 700–880 K. Combined time histories of all carbonyl (–C = O) species, CO and fuel were also measured simultaneously in an effort to study the impact of fuel structure on the concentration and the rate of evolution of first stage ignition products. Of the three isomers studied in this work, n-heptane was found to be the fastest, while 3,3-dimethylpentane was found to be the slowest. The differences in the time scale of formation, and plateau concentration of the intermediates between the isomers across the entire range of test conditions suggests a strong dependency of the measured time histories to fuel structure. These species therefore act as markers of the Negative Temperature Coefficient (NTC) behavior of fuels and can be used as targets for developing semi-empirical, hybrid chemistry models of complex, multi-component petroleum derived gasoline and jet fuels. The time histories reported in this work should prove very useful in the refinement of detailed kinetic models of n-heptane, and development of rate rules for branched alkane isomers.     

Ignition delay times of methane and hydrogen highly diluted in carbon dioxide at high pressures up to 300 atm

The need for more efficient power cycles has attracted interest in super-critical CO₂ (sCO₂) cycles. However, the effects of high CO₂ dilution on auto-ignition at extremely high pressures has not been studied in depth. As part of the effort to understand oxy-fuel combustion with massive CO₂ dilution, we have measured shock tube ignition delay times (IDT) for methane/O₂/CO₂ mixtures and hydrogen/O₂/CO₂ mixtures using sidewall pressure and OH* emission near 306?nm. Ignition delay time was measured in two different facilities behind reflected shock waves over a range of temperatures, 1045–1578?K, in different pressures and mixture regimes, i.e., CH₄/O₂/CO₂ mixtures at 27–286 atm and H₂/O₂/CO₂ mixtures at 37–311 atm. The measured data were compared with the predictions of two recent kinetics models. Fair agreement was found between model and experiment over most of the operating conditions studied. For those conditions where kinetic models fail, the current ignition delay time measurements provide useful target data for development and validation of the mechanisms.     

Supervised learning via smoothed Polya trees

Advances in Data Analysis and Classification - We propose a generative classification model that extends Quadratic Discriminant Analysis (QDA) (Cox in J R Stat Soc Ser B (Methodol)...